Shortening



Patented Dec. 1, 1942 UNITED" STATE s. PATENT OFFICE r snoa'rENnvG Kenneth R. Brown, Tamaqua,la.,

Atlas Powder Company, Wilmin corporation of Delaware assignor to gton, Del., a

No Drawing. Application October 20, 1939,

: Serial N0. 300,359 I 11' Claims.

The present invention relates to improvements in shortenings. V

An object of the invention is to provide a shorteningwhich is useful as a high ratio shortening in baking and also useful as a frying fat.

Another object is. to provide a hydrogenated cottonseed oil shortening'modified' by the addition of a novel emulsifier comprising a partial fatty acid ester of an inner ether derivable from v mannitol.

A further object is to improve hydrogenated cottonseed oil shortening by the addition of a product produced by reacting mannitol drogenated cottonseed oil. v

The above and other objects will be apparent from the specific description setiorth hereinafter.

with hy:

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sugar to flour ratios because they tend to make baking "foolproof.

1 In order to improve shorteningsfor the pur-' pose of makinghigh ratio bakings possible and-to v reduce baking failures as described it has been proposed -to add various emulsifiers to shortenshortenings containing such emulsifiers are satisfactory for baking. Many of these emulsifiers previously employed are relatively ineffective except in relatively high concentrations thus increasing the cost of the improved shortening *objectionably. A further. defect of the improved Shortenings, particularly those designed for 7 household use, are used for two classes jof-purposes, namely, baking and frying. In baking they serve as shortenings, properly so-called,

while in frying they are used as cooking fats.

Unmodified hydrogenated cottonseed oil is largely used as an all-purpose shortening at the present time. It has been recognized however that this unmodified product does not permit the making of sweet baked goods, such as cakes, in which the sugar is present in larger quantities than the flour great quantities of liquids, be used. Particularly in and in which relatively as water or milk, can recent years the advantages of these so-called high ratio cakes have been recognized; A cake having more sugar than fiour is sweeter, has bet-.

ter keeping qualities, remains fresh and keeps its flavor longer, andhas a more uniform texture than one having a ratio of sugar to flour of 1 to 1 (called 100 ratio) or less. However, a ratio of much more than 100 cannot be used where a plain proportions or baking conditions, particularly temperature, or both. With a. high ratio" shortening considerable latitudeis offered in these conditions and there are notably fewer failures in baking. Thus, these improved shortenings are very valuable in cakes of ordinary 55 ening can be prepared by adding to a hydrogen- 7 shortenings of the prior art refers to their lowsmoke points as will be discussed more fully below. The smoke point of a shortening becomes highly important'whenit is used,as household shortenings invariably are,-in1high temperature operations such as frying'and particularly deep fat frying as'used, for example, in cooking doughnuts, French friedpotatoes and the like. Shortenings which have smokepoints below the cooking temperature are practically. useless from the standpoint of the housewife since they'emitj volumes of smoke which soil the walls andjceil'ing j of the kitchen and everything'they contact. It.

household to have only one which must be used both for baking and for frying. Asmentioned, the plain is customary for a type ofcooking fat hydrogenated oil shortenings are useful for both types of operations butheretoforethere has been no high ratio shortening which was capable of use for all purposes. For this reason high ratio shortenings have not been marketed extensively to the household trade.

The present invention produces a, shortening which can be used in baking high ratio cakes and which can also'be used for frying without the objection of excessive smoking. 'All the advantages incident to high ratios in'cakebaking are obtained when it is used. The cakes have excellent volume, texture and flavor and are not sub ject to the falling and shrinkage experienced with unmodified shortenings. The shorteningis'also useful, of course, for use in other types ofbaked I gredient oods like although such as biscuits, pies, 'waflles, bread and the be desired to use more sugar thanflour or, in some of them, any sugar at all. r The same shortening product can be used as a fryingfatfor both pan and deep highly advantageous to both types of work. 7

According to the present invention it has been discovered that an all purposehigh ratio shorthave one material to do with these. other goods it may not fat frying. It is obviousl v nomical to perform.

atm cottonseed oil a few percent of. a novel improving agent. The improver of the invention comprises one or more of the partial esters of -an inner ether derivable from mannitol and a fatty acid derivable from hydrogenated cottonseed oil, which ester or mixture of esters has a hydroxyl number of from 180 to 240. Mannitan mono-stearate, mannitan mono-oleate, mannitan mono-palmitate or mixtures thereof can be used. Such a partial ester can be produced for ex-. ample, by reacting mannitol and theacid, in proper proportions to give a mono-ester, in the shortening will'have' a smoke point below 350 F. and the ester 'will form turbid solutions when dissolved in the shortening.

In the upper end of thebroad range of hydroxyl numbers given the esters may sometimes form slightly turbid solutions when mixed into the shortening but this turbidity is removable by filtering without damage to the improved properties of the shortening. Above a hydroxyl numberof about F2540 however the solutions of the ester in shortening are 'very turbid and frequently 1 cannot be cleared even by repeated filtering, or,

presence of an alkaline catalyst and at about 482? F. so that the mannitol loses water and forms inner ethers, largely mannitamwhich then'react with the fatty acid. Useful mixed esters can be made by using a mixture offatty acids, such as are obtainable by hydrolysis of hydrogenated if cleared, the solution will be found to have lost its properties as a high. ratio shortening.

While it is preferred to form the emulsifier 1 .by alcoholysis as described above it will be apparent to thoseskilled in the art that substancottonseed oil, in the esterification reaction. In 7 each case however the hydroxyl number of the improver must be between 180 and 240 to operate eiiiciently man all purpose shortening. V

While the above described esters or ester inixtures arethe agents responsible for the improve-v ment in -my shortening, I prefer to make the improver bythe reaction of mannitol and hydrogenated cottonseed'oil in which alcoholysis occurs releasing some of the fatty acids which combine with the inner ethers formed by dehydration of mannitol under the conditions .of the reaction. This reaction is produced by heating 1.25 to 2.50

"mols mannitol-to each mol of hydrogenated cot- 7 tonseed oil, in the presence of an alkaline catalyst,-atabout 392 to 572 F. and preferably at v f 392 to"420' F. until the reaction is completed. 7 *After' purifying -to remove the catalyst and any. unreacted ingredients,deodorizing and, if desired, Tdecolorizing, the product has a hydroxyl'number "in the given range. tains predominantly the partial esters off-the The reaction product con tially the same product can be produced by direct esterification; The high ratio shortening is then made by adding'a few percent, say up to 6%, and prefersmall amount is "necessary.

amount of; emulsifier required is lower thanin ably not more than about 4%, by weight of the esterified-product above described to a hydrogenated cottonseed oil shortening. Due to the very high efiiciencyi ot this esteriiied product only a In general the th'e'case of many o'f-the shortening improvers'of the prior art'and' it is therefore an improvement thereover from an economic standpoint.

fattyjacids derivable from-hydrogenated cottonseed foil and the inner 'ethersgderivable from mannitol, principally man'nitan. A product so 7 prepared ispreferable toa pure ester ormixture of pure esters for several reasons. The principal reason is thatthe "product' of the alcoholysis reaction has a 'tast'eand odor more like hydro- .genated cottonseed 'oil, so that its presencezin a' shortening and ultimately in foods doesq-not [modify the normaltaste-thereof. The alcoholysis reaction is also comparatively simple and eco- It is to be understood that the improver for use in this invention can be prepared otherwise than as just described. Numerous other ways of forming such esters willbe apparent to persons skilled in this art. Y

.. It has been found that in order to make a satisfactory all-purpose shortening that is, one that isfree from turbidity and has a smoke point of 350 F. or' higher. the hydroxyl number of the purified ester should be between 180 and 240'and preferably between and 220.

By. the term hydroxylnumber Imean the number of milligrams of potassium hydroxide equivalent to the lhydroxyl content'of onegram The hydrogenated cottonseed oil'referred to herein is preferably a partially hydrogenated material of plastic consistency having an iodine numberof abjout50 to'IO such as the'types sold on the market as'household shortenings.

. The following Examples 1 to 3 illustrate the "preparation of the'reaction product of mannitol and a hydrogenated cottonseed oil.

' EXAMPLE 1 'a 'glass agitator apparatus, an outlet tube and a thermometer. To the above fat were added 113.8 grams mannitol (0.625 mol). and 0.5% NaOH based upon the total reactant weight. The reactants were agitated in an inert atmosphere of CO2 and were brought up to a reaction temperatureiof 428'F. an oil bath was used to heat the reaction flask. After 10 minutes at 428 F. the

, of the washing process is to remove unreacted of fat. oil or wax'as determined in accordance 1 with the method of. Roberts and Schuette, Industrial and Engineering "Chemistry, Analytical Edition, vol. 4,1932, page 257. v X a i If thehydroxyl number "of the ester is below 180 it does not function as an eificient emulsifier in a high ratio shortening for baking purposes.

If the hydroxyl number is above 240 the high ratio '75 mannitan from the reaction product. H2804 is used to decompose the sodium soaps formed by the NaQI-I catalyst. Unwashed esters; even those from which the soap is decomposed and filtered off asinorganic' salt, do not form clear solutions in shortenings and further have smoke points less than 300 F. The washing mixture'was' placed into a separatory funnel. After a few hours thewashing' layer was removed from the ester layer. The ester was washeda second time for five minutes at 212 F., employing. 500 grams 442 grams (aboutf0.5 man of hydrogenated V cottonseed oil, were placed in a'one liter, 3 neck 7 ground glass flask equipped with a C02 inlet tube,

of a 20% sodium sulfate solution, while agitating the mixture by passing a vigorous stream of CO: therethrough. The object of the second wash was to wash out any free H2SO4 left in the product after the first wash. The washing layer was again removed from the ester layer.v The ester layer which contained a small amount of occluded salt and water was deodorized by means of superheated steam for three hours at 320 F. and at a reduced pressure of 5 mm. The ester was cooled in an atmosphere of CO2 to 212 F. and filtered free from its ash.

The above ester had a hydroxyl value of 186. Its smoke point, 3% of ester in a household hydrogenated cottonseed oil shortening, taken in a 7.

Cleveland oil testing apparatus, was 363 F.

EXAMPLE 2 one-half hour at 428 F. The reaction mixture was heated two hours longer at 428 F. The product was then cooled to 212 F. in the inert atmosphere of CO2 and was washed for five minutes at 212 F. with a solution comprising 60 grams anhydrous Na2sO4 and 6 grams concen-' trated H2804 in 240 grams water. After the washing layer was separated from the ester layer,

- the ester was given a second wash with 600 grams of a 20% Nazsol solution for five minutes at 212 F. The ester, after separation from its wash layer, was mixed with a further quantity of the same household shortening equal to about onequarter the weight of ester, and deodorized with steam for three hours at 320 F. under a reduced pressure of 4 mm. The product was given a further treatment with 1% of an activated carbon for one-half hour at 212 F., was cooled in C0: to a temperature of 158 F. and filtered. The smoke point .of the above product, 4% in I. hydrogenatedcottonseed oil shortening was 372 F. The hydroxy number of the ester portion of sparkling clear solutions when dissolved in shortenings.

. EXAMPLE 3 53.5 pounds of hydrogenated cottonseed oil were melted at 122 F. and added to a fifteengallon stainless steel kettle. 0.487 pound of anhydrous NaaCOs' (0.64% of the totalcharge weight) was added. The charge was agitated by mechanical stirrers and also by passing a the above product was 198; The product gave violent stream of CO: through the mixture.

22.3 pounds of mannitol were added at acharge temperature of 122 F. The reactants were heated to 392 F. They formed a uniformly clear product in two hours fifteen minutes after reaching 392 F. The reaction was continued 1.5 hours Nil-2804 solution containing H2SO4,. and secondly with a simple NazSOs solution. The product was deodorized under reduced pressure for three hours at 320 F. with superheated steam. The deodorized product was then given a treatment with 1% of the-activatedcarbon.

The ester portion of theproduct had a hydroxyl valueof 220. Its smoke point, 3% in a household shortening consisting of hydrogenated cotton- I seed'oil, was 362 F. The product'when dissolved in a household shortening consisting of hydrogenated cottonseed oil was very slightly turbid in appearance. However, a simple filtration of this solution through filter paper' produced "a sparkling clear solution.- 6

The productsprepared by any of the Examples 1 to 3 or by other means which will now be readily apparent to one skilled in this'art can bemlxed with a hydrogenated cottonseed oil shortening in the proportion of not more'than' about 6% and preferably not more than 4% of the product. Such an improved shortening can now be used for. baking high ratio cakes and the like as well as for the other conventional uses for-shortening. The smoke points of the completed shortenings will be sufficiently high so that no difilculty will be experienced when these products are used for frying and other high temperature cooking operations. 7

The following examples are intended to illus tr'ate specific formulae for cake baking in which 7 invention is employed.

Exmn: 4 I

The product of Example 1 was mixed with a household shortening consisting of hydrogenated cottonseed oil to form a'mixture containing 3% the product of the of said product. The mixing is advantageously a chocolate cake in accordance with thetormula given below which in the baking trade is termed a ratio formula. Thecake batter'was prepared in separate five minute mixing periods',;the ingredients being added as shown. 7 V

' First mixing period 2 lbs.-8 ozicake flour 1 V 1 lb. 6 oz. of the shortening prepared as described.

These ingredients were admixed preliminarily and then 15 oz. ofchocolate liquorwere added carefully tothe center of the batch to prevent it from sticking to the sides of the mixing bowl.

Second mining period 7 7 To the mixture thus prepared were added 4 lbs. 1 oa'sugar I 1% oz. salt oz. baking soda 9 oz. baking powder a 7 Third mixing period To the mixture thusprepared were-added:

2 lbs. 6 oz. whole eggs 2 lbs. 4oz. whole milk 1 oz. vanilla flavor In the preparation of the batter the ease of mixing and theabsence of curdling were very noticeable. These were attributable to the good mixing qualities 'of the product of Example 1.. I The batter exhibited superior properties as contrasted to a comparative batter made up from a hydrogenated cottonseed oil shortening alone.

Cakes were baked from the batter thus prepared.

' The product of Example'l was mixed with hydrogenated cottonseed oil shortening in such amounts that the said product was present as 3% of thefinished mixture. The mixing can be affected advantageously by'melting the ingredients together, cooling and homogenizing as described in the preceding example. The resulting shorteningwas then employed in the preparation of a T140 r'atiowhite cake. The cake batter was prepared in'separate mixing periods as in Example 4 r in accordance with'the following formula. V

first piisringmeriod f2 lbs, 8 oz', cake fio ur I 1 'lb. 6 oz. of'the shortening prepared as described. ,4 p These ingredientswere mixed 'five minutes. 7 Second raising period To the foregoing. mixture were added:

"1 lb. 14 oz egg whites 1 lb. 6 oz. wholemilk 7 oz. vanilla flavor"- half of which were added and the batter mixed until smooth, the'balance then being added and the batter mixed for five'minutes; The batter was exce'edinglysoftfvery uniform and there wereno signs whatever. of curdling.

Cakes baked from this batter were absolutely uniform throughout and. had a much better, more uniform texture than cakes baked. from the shortening consisting of plain hydrogenated cottonseed oil. 7

Theinvention is not to -be taken as limited to any particular process for preparing the emulsifier. The preferred emulsifier of the invention is a product substantially the same as that produced by the alcoholysis reaction of from about 1.25 to 2.50 mols of mannitoi to 1 mol of hydrogenated cottonseed .oil and having a hydroxyl number of from 180 to 240, and preferably from 195 to 220, after removing the catalyst and unreacted ingredients, and deodorization. The invention contemplates such an emulsifier produced either by alcoholysis or by direct esteriflcation. n v v It. will be apparent that the applicability" of the shortening product accordingto the invention is not limited to the Specific baking examples given and that'these are merely illustrative of the use of the invention.

' I claim:

1. An all purpose shortening comprising hydrogenated cottonseed oil and asmall buteflective amount of a partial ester of mannitan and a fatty acid obtainableby hydrolysis of hydrogen- 'ated cottonseed 011, said mannitan ester having a hydroxyl number of from 180 to 240, said shortening having a smoke point not less than about 350 F. 7

2. An all purpose shortening comprising hydrogenated cottonseed oil and a small but effective amount of a product comprising a partial ester of mannitan and the mixed fattyacids obtainable by hydrolysis of hydrogenated cottonseed oil, said product having a hydroxyl number of from 180 to 240, and said shortening having a smoke-pointnot less than about 350"v F.

3. An all purpose shortening comprising hy-,

drogenated cottonseed oil and a small but effective amount of an improver consisting predominantly of mannitan partial esters of fatty acids obtainable by hydrolysis of hydrogenated cottonseed oil, said improver having a hydroxyl numening havinga smoke point not less than about 4. An all purpose shortening as defined in claim 3 wherein the shortening contains not more than about 6% of said improver.

5. An all purpose shortening as defined in claim 3 wherein the shortening contains not more than about 4% of said improver.

'6. An all purpose shortening comprising hydrogenated cottonseed oil, and a small but effective amount of an improver consisting predominantly of mannitan partial esters of fatty acids obtainable by hydrolysis of hydrogenated cottonseed oil, said improver having a hydroxyl number of from 195 to 220 and being produced by reacting from 1.25 to 2.50 mols of mannitol with 1 m'ol of hydrogenated cottonseed oil, said shortening having a smoke point not less than about 350 F. andbeing free from turbidity.

'7. A shortening as defined in claim 6 wherein the said improver is present in the proportion of not more than about 6% of the shortening.

8. A shortening as defined in claim 6 where- I in the said improver is present in the proportion of not morethan about 4% of the shortening.

9. A shortening improver miscible with a hydrogenated cottonseed oil shortening to produce a high ratio shortening with a smoke point not less than about 350 F., comprising a mannitan partial ester of fatty acid obtainable by hydrolysis of hydrogenated cot'tedseed oil, said ester havingahydroxyl value of from 180 to 240.

101 A shortening improver miscible with a hydrogenated cottonseed oilshortening to produce a high ratio shortening with a smoke point not less than about 350 F., said improver consisting predominantly ofmannitan partial esters of fatty acids obtainable by hydrolysis of hydrogenated cottonseed oil, said improver having a hydroxyl number of from 180 to 240 and being produced by reacting from 1.25 to 2.50 m'ols of man- 

